CN107108806A

CN107108806A - The copolymer of 1,3,3,3 tetrafluoropropenes

Info

Publication number: CN107108806A
Application number: CN201580067292.3A
Authority: CN
Inventors: 彭晟; 曾凡令; 洪明泓; R.E.尤肖尔德
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2014-12-09
Filing date: 2015-12-01
Publication date: 2017-08-29
Also published as: EP3230329A1; US20170342177A1; US10364311B2; JP2017537208A; WO2016094121A1

Abstract

The invention provides 1,3,3,3 tetrafluoropropene (HFO 1234ze) copolymer, it includes 1,3,3,3 tetrafluoropropenes and one or more comonomers in the following：PVF (VF), vinylidene fluoride (VF₂), tetrafluoroethene (TFE), CTFE (CTFE), hexafluoropropene (HFP) and perfluor (alkyl vinyl ether) (PAVE), wherein described alkyl contains 1 to 5 carbon atom, the copolymer is fluoroplastics or fluoroelastomer, is specifically dependent upon content of monomer.

Description

The copolymer of 1,3,3,3- tetrafluoropropene

The cross reference of related application

U.S. Provisional Application 62/89,329 that patent application claims were submitted on December 9th, 2014 and in January, 2015 The rights and interests for the U.S. Provisional Application 62/101,096 submitted for 8th, these provisional applications are incorporated by reference in its entirety herein.

Background technology

Technical field

The present invention relates to HFO-1234ze (CF₃CH=CHF, 1,3,3,3- tetrafluoropropene) and other copolymerizable fluorinated monomers Polymerization and the HFO-1234ze copolymers that are obtained.

The description of association area

The need for U.S. Patent Publication 2012/0208007 is solved to the barrier coatings on reflecting layer, the barrier coatings quilt The back side of substrate of glass is applied to protect the reflection characteristic in reflecting layer.The curtain coating provided in the bibliography is thermosetting Polymer, the thermosetting polymer, which contains, largely has formula-[CR₁CF₃-CR₂R₃]-polymer segment polymer, wherein R₁、 R₂And R₃Independently selected from H and F [0010].Various HF hydrocarbons (HFO) can be used for forming polymer, HFO-1234yf (2,3,3, 3- tetrafluoropropenes, CF₃CF=CH₂) it is disclosed as suitable compound [0025].Other suitable compounds are HFO-1234zf (CF₃CH=CH₂), HFO-1234ze and HFO-1225 (pentafluoropropene) [0026].These compounds can with additional monomer copolymerization, Mention about 25 kinds of such monomers [0027].Unique example uses 1234yf solution as coating composition.

The need for United States Patent (USP) 8,163,858 is solved to damp-proof layer and oxygen barrier layer, and it is common with fluorination there is provided containing The film of the vinylidene fluoride of polycondensation monomer copolymerization as barrier, the film contain 50 weight % to 99 weight % vinylidene fluoride with In oxygen barrier layer and vinylidene fluoride containing 0.1 to 50 weight % for damp-proof layer, the amount of fluorinated comonomers is respectively 0.1 weight % to 50 weight %, and 50 weight % to 99.9 weight % (the 2nd row, 18-36 rows).It is preferred that fluorinated copolymerizable Monomer is 2,3,3,3- tetrafluoropropenes, 1,1,3,3,3- pentafluoropropene, the chloro- pentafluoropropenes of 2-, hexafluoropropene, trifluoro-ethylene, three Fluorine vinyl chloride, 3,3,3- tri- fluoro- 2- trifluoromethyls propylene, and their mixture (the 3rd row, 33-37 rows).Other fluorinations Comonomer be disclosed as can the amount of appropriateness use, mention more than comonomer as 40 kinds, including 1234ze's is cis Isomers and transisomer.HFO-1234yf is the unique HFO used in the vinylidene fluoride copolymer of example.

It is chloro- that U.S. Patent Publication 2014/008987 discloses 2,3,3,3- tetrafluoropropenes, 1,3,3,3- tetrafluoropropenes or 1- The copolymerization [0007] of 2,3,3- tetrafluoropropenes and ethylenically unsaturated monomers.Hydrocarbons ethylenically unsaturated monomers are together with HFP mono- Disclosure is played, ethylenically unsaturated monomers account for 30 to 95 moles of % [0009] of copolymer, [0100].Example all referring to 2,3,3, The copolymerization of 3- tetrafluoropropenes (1234yf) and ethene.

Obviously, from ' 007 and ' lack in 858 to contain HFO-1234ze as comonomer fluoropolymer pay close attention to Any reason.

The content of the invention

It has been found that HFO-1234ze has the copolymerized ability that HFO-1234yf does not have.It has also been found that, HFO-1234ze with Speed copolymerization more faster than hexafluoropropene, hexafluoropropene is present in many fluoropolymers, i.e. fluoroplastics and fluoroelastomer. It has furthermore been found that once in incorporation fluoropolymer (instead of hexafluoropropene), the heat endurance of fluoropolymer will be improved.

These are found and other advantages are embodied in the HFO-1234ze copolymers of the present invention, and it can be described as including 1, The copolymer of 3,3,3- tetrafluoropropenes (1234ze) and one or more comonomers in the following：PVF (VF), vinylidene fluoride (VF₂), tetrafluoroethene (TFE), CTFE (CTFE), hexafluoropropene (HFP) and perfluor (alkyl Vinyl ethers) (PAVE), wherein the alkyl contains 1 to 5 carbon atom.

Copolymer can be fluoroplastics or fluoroelastomer, and this depends on monomer content.

When copolymer is fluoroelastomer, 1234ze is the cure sites of fluoroelastomer.1234ze monomers are as altogether The function of cure sites in polymers can be described as including the method for procedure below：Formed by copolymerization and include 1,3,3,3- tetra- The copolymer of fluoropropene (1234ze) and one or more comonomers in the following：PVF (VF), inclined difluoro Ethene (VF₂), tetrafluoroethene (TFE), hexafluoropropene (HFP) and perfluor (alkyl vinyl ether) (PAVE), wherein the alkyl Contain 1 to 5 carbon atom；And solidify the copolymer.

In one embodiment, 1234ze, which may be present in, replaces some or all of HFP in copolymer.When HFP connects When being present in together in copolymer with 1234ze, then there is preferably can be total to at least one other of 1234ze and HFP copolymerization Polycondensation monomer, it is therefore preferable to fluoroolefins, more preferably VF₂And/or TFE.

In another embodiment, copolymer includes 1234ze and VF.Preferably, the amount of the 1234ze in copolymer is At least 18 moles %.

In another embodiment, copolymer includes 1234ze, VF and TFE.

In another embodiment, copolymer includes 1234ze, TFE and VF₂, and optional HFP.

In another embodiment, copolymer includes 1234ze, TFE, and optional HFP.

In another embodiment, copolymer includes 1234ze, TFE and ethene, and optional HFP.

In another embodiment, copolymer includes 1234ze, CTFE and ethene or 1234ze, CTFE, TFE and second Alkene, any copolymer optionally includes modified monomer described below.

In another embodiment, copolymer includes 1234ze, TFE, VF₂, and optional HFP.

In another embodiment, copolymer is fluoroelastomer, and it includes 1234ze and VF₂Or perfluor (alkyl Any one of vinyl ethers) (being preferably perfluor (methyl vinyl ether) (PMVE)).In the preferred aspect of the embodiment, Copolymer (fluoroelastomer) includes 1234ze, VF₂, TFE, and optional HFP.Preferably, copolymer (the fluorine-containing elasticity Body) additionally comprise HFP.In another preferred aspect of the embodiment, 1234ze/VF₂/ TFE copolymer (fluoroelastomer) is another Perfluor (alkyl vinyl ether) is included outside, it is therefore preferable to PMVE.In another embodiment, copolymer (fluoroelastomer) is wrapped Containing 1234ze, TFE and perfluor (alkyl vinyl ether), it is therefore preferable to PMVE.

The example of the copolymer of the present invention includes the following：

Fluoroplastics：

1234ze/VF

1234ze/VF/TFE

1234ze/TFE

1234ze/TFE/HFP

1234ze/TFE/ ethene

1234ze/TFE/HFP/ ethene

1234ze/CTFE/ ethene

1234ze/CTFE/TFE/ ethene

1234ze/TFE/VF₂

1234ze/TFE/VF₂/HFP

1234ze/VF₂

Fluoroelastomer：

1234ze/VF₂

1234ze/VF₂/HFP

1234ze/VF₂/TFE

1234ze/VF₂/TFE/HFP

1234ze/VF₂/TFE/PMVE

1234ze/TFE/PMVE

It is present in the monomer in these fluoroplastics and fluoroelastomer to exist to obtain pointed plastics with effective amount Or elastomer properties.

Embodiment

It can be cis-isomer or trans isomer configuration for the HFO-1234ze in the present invention or can be that these are different The mixture of structure body.

For simplicity, copolymer of the invention is described with monomer, obtains described common from the monomer by copolymerization Polymers.These monomers are present in copolymer as repeat unit, such as are-CF for TFE₂-CF₂-, for VF be-CH₂- CHF-, for VF₂For-CH₂-CF₂-, for HFP be-CCF₃-CF₂-, for PMVE be-CF2-CFOCF₃-, for CTFE for- ClFC-CF₂-, and be-CHCF for 1234ze₃-CHF-。

Term copolymer used herein includes the polymer comprising two or more comonomers.Therefore, this hair Bright 1234ze copolymers include 1234ze and the copolymer of at least one additional comonomers.Term copolymer is common including binary Polymers, terpolymer, quadripolymer, and even contain the copolymer of greater number of comonomer.

With reference to the copolymer of the present invention：Transitional term " including ", " including ", " having ", " containing " or its any other change Type form covers except the presence of comonomer in the copolymer in addition to those particularly pointed out.Transition phrase " is by ... group Into " exclusion has such additional comonomers in the copolymer.Transition phrase " substantially by ... constitute " is included except on literal Comonomer outside those disclosed, precondition is that these comonomers comprised additionally in will not be substantially influenceed by right The basic and novel feature of claimed invention.Term " substantially by ... constitute " occupy " including " and " by ... constitute " It is middle.Although the preferred transitional term of the copolymer of the present invention is " including " as described above etc., but it is also possible to be susceptible to transition Term " by ... constitute " wait or " substantially by ... constitute " can be applied to one or more of these copolymers or whole.

Term elastomer in fluoroelastomer refers to the copolymer for showing rubbery character, that is, is being stretched to high drawing Its original-shape can be recovered after rate (for example, at least 50%).Copolymer is considered as fluoroelastomer, either in polymerization Still its rubber elastomer characteristics is only shown after hardening.On the contrary, fluoroplastics are not rubber, but rigid and thin portion It is flexible to divide.

Relative to fluoroplastics：

1234ze and VF preferred fluoroplastics copolymer includes the two of 1234ze and VF and at least one additional comonomers Membered copolymer and copolymer, at least one additional comonomers can be with 1234ze and VF copolymerization.Preferably, additional copolymerization list Body is fluoroolefins, preferably containing at least two carbon atoms on the carbon atom for substituting onto the part as copolymer chain. It is preferred that bipolymer be 1234ze/VF.Preferably, the 1234ze and 98 that the composition of bipolymer is 2 to 40 moles of % To 60 moles of % VF, the combination of 100 moles of % these comonomers altogether is reached.When being used in the copolymerization with VF 1234yf is replaced during 1234ze, is limited by the amount with the 1234yf of VF copolymerization so that gained copolymer, which contains, to be no more than 14 moles of % 1234yf.Even if work as excessive 1234yf to be present in interpolymerization medium, and in order to promote 1234yf copolymerization And when taking measures, the maximum with VF copolymerization is 14 moles of %.Accordingly, it is preferred that 1234ze/VF compositions are wherein 1234ze Constitute 15 to 40 moles of % and VF constitutes 5 to 60 moles of %, reach the combination of 100 moles of % these comonomers altogether.

1234ze and VF another preferred fluoroplastics copolymer is the copolymer for including 1234ze/VF/TFE.Preferably, The composition of the copolymer is 1 to 25 mole of % 1234ze, 20 to 85 moles of % VF and 10 to 80 moles of % TFE, is reached The combination of 100 moles of % these monomers altogether.Another preferred copolymer is to include 1234ze/VF/TFE/VF₂Copolymerization Thing, wherein composition is 1 to 25 mole of % 1234ze, 20 to 85 moles of % VF and 10 to 80 moles of % TFE and VF₂Group Close, reach the combination of 100 moles of % these monomers altogether.TFE and VF in copolymer₂The combination of monomer be preferably 10 to 90 moles of % every kind of monomer, reaches this combination of 100 moles of % these monomers altogether.

Many (including terpolymer and quadripolymer) in these 1234ze/VF copolymers be heated to 75 to Dissolved at 100 DEG C in DMF (dimethylformamide) or DMAC (dimethyl acetamide).Resulting solution can be poured on surface And dry the film that can be separated to be formed with surface or coating on the surface.Film or coating show high durable in outdoor exposure Property.Resulting solution is to can be used for semi-conductor industry, the solvent based coating of electronics industry, the finish paint of photoresist, anti-reflective coating Material, wire coating, oil gas protective coating and photovoltaic.

Copolymer with high TFE contents can by the method for such as extrusion and injection molding etc melting manufacture film forming and Other can be used for the shape of outdoor environment.

1234ze/TFE preferred fluoroplastics copolymer, which includes having, to be added with least one of 1234ze and TFE copolymerization The bipolymer and copolymer of comonomer.Preferably, additional comonomers are fluoroolefins, are preferably turned into containing substituting onto At least two carbon atoms on the carbon atom of a part for copolymer chain.Alternatively, additional comonomers can be ethene.Binary Copolymer analog is similar to well-known fluoroplastics FEP, and it includes TFE and HFP copolymer, and difference is, 1234ze generations For all HFP, and assign the faster copolymerization rate of 1234ze/TFE copolymers of gained and improved heat endurance.By altogether Repeat unit-CHCF of the polyacene derivative from 1234ze₃- CHF- does not produce the heat shakiness produced by the connection end to end of HFP repeat units Fixed-CF₃CF--CF₃CF- dyads.United States Patent (USP) 4,626,587 discloses the heat endurance of the dyad.Preferably, copolymerization 1234ze and 99 to 80 mole % of the composition comprising 1 to 20 mole of % of thing TFE, reach these lists of 100 moles of % altogether The combination of body, the TFE of 1234ze and 98 to 90 moles of % more preferably comprising 2 to 10 moles of %, reaches 100 moles of % altogether These monomers combination.In another embodiment, 1234ze is present in the only a part that HFP is replaced in copolymer, by This gained copolymer includes 1234ze/TFE/HFP.Two embodiments can be described as comprising 1234ze, TFE and optionally HFP copolymer, 1234ze and if there is HFP combined amount be 1 to 20 mole of %, and 1234ze and if there is Each of HFP is at least 0.1 mole % amount, and TFE exists with 80 to 99 moles of % amount, based on 1234ze, TFE and such as The combination mole % meters for the HFP that fruit is present reach 100 moles of % altogether.It is highly preferred that copolymer comprising 1234ze, TFE and Optional HFP, 1234ze and if there is HFP combined amount be 1 to 10 mole of %, and 1234ze and if there is Each of HFP is at least 0.1 mole % amount, and TFE exists with 90 to 99 moles of % amount, based on 1234ze, TFE and such as The combination mole % meters for the HFP that fruit is present reach 100 moles of % altogether.In preferred embodiments, HFP rubs with least 0.1 Your % amount, preferably with 0.5 mole of % amount, up to above-mentioned 20 moles of % and 10 mole of % maximum, and it is more excellent No more than 5 moles % of selection of land are present, and 12134ze, which makes up, reaches above-mentioned 20 moles of % or 10 mole of the maximum amount of differences of % altogether.

1234ze/TFE copolymers and 12324ze/TFE/HFP copolymers can also be all comprising a small amount of additional fluorochemical monomer Such as perfluor (ethyl vinyl ether) or perfluor (propyl vinyl ether), to improve the MIT flex lives of copolymer.It is this small amount of Fluoroolefins is 0.2 to 3 weight % of copolymer gross weight.

Another embodiment of 1234ze/TFE copolymers be comprising 1234ze/TFE/ ethene and optional HFP or PFBE (perfluorobutyl ethylene, CF₃(CF₂)₂CH=CH₂) copolymer.The embodiment has two aspects.Suitable for this two The composition of aspect is 0.1 to 10 mole of % 1234ze, 1 to 95 mole of % TFE and 2 to 60 moles of % ethene.

According on one side, 1234ze replaces some in the PFBE modifying agent of ETFE (ethylene/tetrafluoroethylene) copolymer Or all.Modifying agent to be present in ETFE copolymers to improve stress cracking resistance on a small quantity.Based on 100 moles of %'s altogether 1234ze, TFE and the combination mole % of ethene meters, the 1234ze preferably constituted as 0.1 to 10 mole of % of this aspect, 40 to 60 Mole % TFE, and 40 to 60 moles of % ethene.This aspect is contemplated that not all PFBE all by 1234ze generations Replace, thus copolymer is that, with the 1234ze/PFBE/TFE/ ethene preferably constituted same as described above, difference is, 1234ze and PFBE constitutes 0.1 to 10 mole of % part of copolymer.Preferably, 1234ze constitutes the molal quantity for constituting the part At least 20%, and constitute at least 0.1 mole % of total precursor copolymer.These copolymers have the ETFE with being modified with PFBE Copolymer identical purposes, such as wire insulation.

According to the another aspect of the embodiment, 1234ze, which is present in copolymer, to be replaced in copolymer TFE/HFP/ ethene Some or all of HFP.The 1234ze preferably constituted as 2 to 60 moles of % of the copolymer, 1 to 95 mole of % TFE With 2 to 60 moles of % ethene, the combination of 100 moles of % these monomers altogether is reached.When HFP is existed in copolymer When, 1234ze and HFP combination adds up to 2 to 60 moles of %, and the amount of TFE and ethene is same as described above.1234ze and HFP are preferred Ground each constitutes at least the 1% of the 1234ze and HFP of combination 2 to 60 moles of %, and the 1234ze more preferably combined and At least the 2% of HFP total moles %, precondition is the group of 1234ze, TFE, HFP based on 100 moles of % altogether and ethene A mole % meters are closed, copolymer includes at least 12 moles % 1234ze, preferably at least 3 moles % 1234ze.Copolymer Another 1234ze preferably constituted as 2 to 25 moles of %, 60 to 95 moles of % TFE and 2 to 25 moles of % ethene, reach total The combination of totally 100 moles of % these monomers.Preferably constituted for this, when HFP is existed in copolymer, 1234ze and HFP combination adds up to 2 to 25 moles of %, and the amount of TFE and ethene is same as described above.1234ze and HFP are preferably each constituted At least the 1% of the 1234ze and HFP of combination 2 to 25 moles of %, and the 1234ze that more preferably combines and HFP always rub At least the 2% of your %, precondition is 1234ze, TFE, HFP based on 100 moles of % altogether and the combination mole % of ethene Meter, copolymer includes at least 2 moles % 1234ze, preferably at least 3 moles % 1234ze.The 1234ze/ of the present invention TFE/ ethene and 1234ze/TFE/HFP/ ethylene copolymers are preferably unbodied, i.e., without low crystallinity so that it Can be melted and be manufactured into hyaline membrane.They also have low-k, film is can be used as insulator in electronic application.

Even if at high temperature, 1234ze/TFE copolymers are also insoluble in varsol, but by such as extruding and being injected into The molding technique of type etc is melted the shape for being manufactured into such as film and pipe etc, so as to with FEP identical mode applications.

It is preferred that another embodiment of fluoroplastics copolymer be such copolymer, wherein 1234ze replaces ECTFE Some or all of HFIB (hexafluoro-isobutene) stress cracking modifying agent of (ethene/CTFE) copolymer.Based on total Totally 100 moles of % combination mole % meters, the copolymer preferably constitutes the ethene comprising 40 to 60 moles of %, 40 to 60 rubbed Your % CTFE or CTFE and TFE and 0.1 to 10 mole of % 1234ze.CTFE components can account for CTFE and TFE molal quantity Overall 40 to 60 moles of % or up to 80%, so as to constitute this 40 to 60 moles of % of copolymer component.Therefore, this is total to Polymers can be 1234ze/CTFE/ ethene or 1234ze/CTFE/TFE/ ethene.Any of these copolymers can also be included HFIB replaces a part for 0.1 to 10 mole of % 1234ze components.For example, HFIB can replace the molal quantity of 1234ze components At least 20%, precondition is that the minimum content of the 1234ze in copolymer is at least 0.1 mole %, it is therefore preferable at least 0.5 Mole %.Therefore, (presence of TFE and HFIB wherein in copolymer are to appoint independently of one another to the copolymer of the embodiment Choosing) 1234ze/CTFE/ ethene/HFIB and 1234ze/CTFE/TFE/ ethene/HFIB copolymers are susceptible to, and do not have TFE or HFIB these copolymers.The copolymer of the embodiment of the present invention can be used as the corrosion resistant in the substrate of corrosion-susceptible Lose coating.

1234ze/VF₂Preferred fluoroplastics copolymer include have can be with 1234ze and VF₂At least one of copolymerization is added The bipolymer and copolymer of comonomer.Preferably, additional comonomers are fluoroolefins, are preferably turned into containing substituting onto At least two carbon atoms on the carbon atom of a part for copolymer chain.Preferably, the composition of bipolymer rubs for 2 to 35 Your % 1234ze and 98 to 65 moles of % VF₂, reach the combination of 100 moles of % these comonomers altogether.Preferably, Copolymer includes 1234ze, TFE, VF₂And optional HFP.1234ze, which may be present in, replaces TFE/VF in copolymer₂/ HFP is common Part or all of the HFP found in polymers.Copolymer 1 234ze/VF₂/ TFE's preferably constitutes as 2 to 20 moles of %'s 1234ze, 15 to 50 moles of % VF₂With 20 to 80 moles of % TFE, the group of 100 moles of % these monomers altogether is reached Close.Copolymer 1 234ze/VF₂Preferably constituting for/TFE/HFP is identical with 1234ze/VF2/TFE copolymers, and difference is 2 1234ze to 20 moles of % is applied to 1234ze and HFP combination.Relative to 1234ze/HFP combinations, the 1234ze existed Amount be 10 to 90 moles of %, and the HFP existed amount is 90 to 10 moles of %, reaches 100 moles of % monomer altogether Combination.These copolymers are melted the shape for being manufactured into such as film etc by the molding technique of such as extrusion and injection molding etc Shape is to coat, or such as shape of pipe etc is so as to trandfer fluid.

Relative to fluoroelastomer：

It is preferred that fluoroelastomer be include 1234ze/VF₂And the Tg shown is not more than 5 DEG C, and preferably not Copolymer more than 0 DEG C.1234ze comonomers represent the cure sites of fluoroelastomer.Bipolymer 1234ze/VF₂It is excellent Selection of land has 5 to 35 moles of % 1234ze and 95 to 65 moles of % VF₂Composition, reach 100 moles of % altogether these The combination of monomer.1234ze/VF₂Preferred copolymer comprising can be with 1234ze and VF₂At least one additional monomer of copolymerization.It is excellent Selection of land, additional comonomers are fluoroolefins, preferably containing on the carbon atom for substituting onto the part as copolymer chain At least two carbon atoms.It is preferred that additional monomer be one or more in HFP, TFE and PMVE.

It is preferred that fluoroelastomer include with consisting of 1234ze/VF₂/HFP：(1234ze+HFP)/VF₂=(30 100 moles of % (combination identity phases with reaching 100 moles of % these monomers altogether altogether are reached to 15)/70 to 85 mole % Together).Preferably, 1234ze account for that 5 to 95% and HFP accounts for 95 to 5% and reaches 30 to 15 moles of % altogether 100%, more preferably Ground, 1234ze is 10 to 90% and HFP is 90 to 10% to reach altogether the 100% of 30 to 15 moles of %.

Another preferred fluoroelastomer includes the 1234ze/VF with consisting of₂/TFE：1234ze/VF₂/ TFE= 15 to 25/50 to 80/7 to 30 moles of % reach 100 moles of % altogether.

Another preferred fluoroelastomer includes the 1234ze/VF with consisting of₂/TFE/HFP：(1234ze+ HFP)/VF₂/ TFE=(15 to 25)/50 to 80/7 to 30 moles of % reaches 100 moles of % altogether.Preferably, 1234ze account for 5 to 95% and HFP account for 95 to 5% reach 15 to 25 moles of % altogether 100%, it is highly preferred that 1234ze be 10 to 90% and HFP is 90 to 10% to reach altogether the 100% of 15 to 25 moles of %.

Another preferred fluoroelastomer includes the 1234ze/VF with consisting of₂/TFE/PMVE：1 to 40 mole of % 1234ze, 15 to 60 moles of % VF₂, 5 to 25 moles of % TFE and 15 to 40 moles of % PMVE, reach and 100 rub altogether The combination of your % these monomers.

It is same that there are no more than 5 DEG C, preferably not more than 0 DEG C of Tg another preferred elastomer includes 1234ze/ TFE/PMVE, it is preferably that 0.1 to 5/55 to 65/35 to 45 mole of % reaches 100 moles of % altogether that it, which is constituted,.

Fluoroelastomer during copolymerization be typically natural gum, the natural gum can such as by as needed with supplementary element be compounded and It is impregnated in, then solidifies to show rubbery character.Solidification is carried out in the following manner：(it is preferably by curing agent The curing agent to carry out cross-linking reaction with the 1234ze monomers being present in copolymer of nucleophilic) mix in copolymer, and Heating gained copolymer/curing agent mixture.Before heating, the copolymer of compounding is formed as to the required shape of product to be solidified Shape.

Include granular filler such as barium sulfate or titanium dioxide for such supplementary element for being compounded into copolymer, acid by Body such as metal oxide (such as magnesia or calcium hydroxide), curing agent such as ethylenediamine carbamate, hexa-methylene two Amine carbamate, trien/benzoyl peroxide and N, N '-- phenylene dimaleimide.Additional hardener Have disclosed in example 2 below 3.Then can by normative heat treatment by the copolymer of compounding be formed as such as seal, The shape of packing ring, O-ring and flexible pipe etc, then carries out solidify afterwards under high temperature such as 450 °F (232 DEG C).

The copolymerization process of 1234ze copolymers to prepare the present invention is carried out preferably as in following examples, with Random copolymer is produced, i.e., is not programmed into polymerisation to produce block copolymer by monomer feed.

With the typical large-scale methods of 1234ze copolymers for forming the present invention it is to contain fluorochemical surface for copolymerization Aqueous dispersion polymerization is carried out to monomer in the agitating and heating reactor of activating agent, radical initiator and deionized water.With poly- Close and carry out, additional monomer is added to keep pressure, together with the additional charging for carrying out surfactant and initiator.Chain-transferring agent can For the copolymerization of some polymer to control molecular weight.In order to terminate copolymerization, stop all chargings, empty reactor and use nitrogen Purging, and the material copolymerization thing dispersion in reactor is transferred in cooling container.In order to available for metal, glass and knit In the coating of thing, generally polymeric dispersions are transferred to during dispersion concentration operation, this can be made as the steady of coating Determine dispersion.Alternatively, copolymer dispersion is condensed, and the copolymer of condensation is separated with aqueous medium and dried to obtain Copolymer powder, then can be used for article of manufacture by the copolymer powder in the following manner：Such as compacting is manufactured or moulded with regard to fluorine Melt-processed is carried out for material, solidify afterwards are then carried out for fluoroelastomer.

Embodiment

Heat stability testing-and in the test, the heat endurance of copolymer is determined by heating the sample of copolymer, During this, the % losses of measurement weight.Temperature is higher before weight % losses reach 5 weight %, and the heat endurance of copolymer is higher. Heat stability testing is carried out using Q50TGA (thermogravimetric analyzer) instrument of TA instrument companies (TA Instruments).By with 10 DEG C/min of speed heating copolymer sample (10 to 15 milligrams), from room temperature to being tested under 500 DEG C of air.Prison Survey and record the weight loss of sample.The temperature that weight loss reaches 5 weight % can be calculated from the record.

Embodiment 1 is to 8-VF/TFE/1234ze copolymers

To 400mLIn C oscillating tubes load distilled water (200mL),FS-10 (5.30g), phosphorus Sour disodium hydrogen (1.3g) and ammonium persulfate (0.16g), cooling, is emptied and nitrogen is rinsed.Then fluorine second is loaded into oscillating tube Alkene (3.125g), tetrafluoroethene (50g) and 1,3,3,3- tetrafluoropropenes (9.4g).Start oscillating tube to be aggressively shaken, and Continue in whole service.Oscillating tube is heated to 70 DEG C so that the pressure in autoclave from 260 increase to 645psi (1.8 to 4.5MPa).Stop within 18 minutes shaking and heating after pressure reduces by 21% to 513psi (3.5MPa).This produces polymer breast Liquid, the polymer emulsion by adding 100ml saturation MgSO with vigorous stirring₄The aqueous solution and condense.It is collected by filtration The polymer of precipitation, and washed for several times with warm water (70 DEG C).After being dried 24 hours in 80 DEG C of vacuum drying ovens (100mmHg), obtain Obtain 28g white polymer.

Polymer analysis：

DSC, 10 DEG C/min, N₂, second of heating：It is 288 DEG C that Tm, which is 199 DEG C and Tm,.Composition¹⁹F NMR (mole %)： VF/TFE/1,3,3,3- tetrafluoropropene terpolymers (15.74/78.4/5.86).Reactor (enters monomer during copolymerization Expect in the reactor) in copolymerization produce with single melting temperature (Tm) copolymer.

Identical experimental arrangement is applied to embodiment 2 to 8, and the results are shown in Table 1.

Table 1：VF-TFE-1,3,3,3- tetrafluoropropene terpolymers

The copolymer of embodiment 4 shows highest heat endurance, by the copolymerization produce of the 1234ze containing maximum amount It is raw, although the copolymer contains the TFE of substantial amounts of VF and relatively small amount.The copolymer of embodiment 4 does not have melting temperature, and this shows In the absence of crystallinity.The reaction time (time that pressure declines) of all copolymers of embodiment 1 to 8 is short, and this shows in copolymerization 1234ze high response.Copolymer does not dissolve in varsol at a temperature of environment temperature (about 20 DEG C), but is dissolved in and is heated to 75 DEG C temperature DMF and DMAC in.

Embodiment 9 is to 12HFP-TFE-1234ze copolymers

To 400mLIn C oscillating tubes load distilled water (200mL),FS-10 (5.30g), phosphorus Sour disodium hydrogen (1.3g) and ammonium persulfate (0.16g), cooling, is emptied and nitrogen is rinsed.Then hexafluoro is loaded into oscillating tube Propylene (3.5g), tetrafluoroethene (50g) and 1,3,3,3- tetrafluoropropenes (17g).Start being aggressively shaken for oscillating tube, and whole Continue in individual operation.Oscillating tube is heated to 70 DEG C so that the pressure in autoclave from 192 increase to 572psi (1.3 to 3.9MPa).Stop within 33 minutes shaking and heating after pressure reduces by 21% to 458psi (3.2MPa).This produces polymer breast Liquid, the polymer emulsion is condensed by adding the 100ml saturation MgSO4 aqueous solution with vigorous stirring.It is collected by filtration The polymer of precipitation, and washed for several times with warm water (70 DEG C).After being dried 24 hours in 80 DEG C of vacuum drying ovens (100mmHg), Obtain 24.1g white polymers.

Polymer analysis：

DSC, 10 DEG C/min, N₂, second of heating：Tm is 289 DEG C

Composition¹⁹F NMR (mole %)：HFP/TFE/1,3,3,3- tetrafluoropropene terpolymers

(0.5/95.66/3.84)

Identical experimental arrangement is applied to embodiment 10 to 12, and the results are shown in Table 2.

Table 2：HFP-TFE-1,3,3,3- tetrafluoropropene terpolymers

HFP-TFE-1, the tetrafluoropropene of 3,3,3- tetrafluoropropene terpolymer (table 2) as shown by data 1,3,3,3- and TFE Reaction be faster than HFP.By the way that with the increase of HFP contents, the time (reaction time) that pressure declines increases, and this shows that 1234ze contains The change of amount is relatively small.The loss of 5% polymer weight shows in air, in 1,3,3,3- tetrafluoropropene content increase, three Membered copolymer more thermal-stable.The composition of the polymer with highest 1234ze contents of embodiment 9 shows to reach in weight loss The maximum temperature reached before to 5 weight %.The copolymer of embodiment 9 to 12 is all insoluble in varsol, including is heated to The DMF and DMAC of 75 to 100 DEG C of temperature.

Embodiment 13 to 18：VF-1234ze copolymers

Into 400mL Hastelloy C oscillating tubes load distilled water (200mL),31R1 (0.1g) and Vazo-50 (0.05g), cooling, is emptied and nitrogen is rinsed.Then PVF (90g) and 1,3,3,3- are loaded into oscillating tube Tetrafluoropropene (10g).Start being aggressively shaken for oscillating tube, and continue in whole service.Oscillating tube is heated to 80 DEG C, from And the pressure in autoclave is increased to 1240psi (1.2 to 8.6MPa) from 168.20% to 981psi is reduced in pressure Stop shaking and heat within 33 minutes after (6.9MPa).This produces polymer emulsion, and the polymer emulsion is by being stirred vigorously The lower addition 100ml saturation MgSO4 aqueous solution and condense.It is collected by filtration the polymer of precipitation, and with warm water (70 DEG C) Washing is for several times.After being dried 24 hours in 80 DEG C of vacuum drying ovens (100mmHg), 47g white polymer is obtained.

Polymer analysis：

DSC, 10 DEG C/min, N₂, second of heating：It is 179 DEG C of compositions that Tg, which is 44 DEG C and Tm,¹⁹F NMR (mole %)： VF/1,3,3,3- tetrafluoropropene copolymers (97.9/2.1).

Identical experimental arrangement is applied to embodiment 14 to 18, and the results are shown in Table 3.

Table 3：VF-1,3,3,3- tetrafluoropropene copolymers

Copolymer is dissolved at ambient temperature all insoluble in varsol and is heated to 75 to 100 DEG C of DMF and DMAC In.

Under the same conditions, with VF-2,3,3,3- tetrafluoropropenes (HFO-1234yf) carry out identical serial experiment.2,3, 3,3- tetrafluoropropenes are incorporated under 13 to 16 moles of % and flattened out.The a greater amount of 1234yf being added in reactor will not cause altogether The increase of 1234yf incorporations in polymers is more than 16 moles of %.When attempting to increase the maximum incorporation, by 1234yf with this It will not increase in maximum incorporation copolymer with the change made to copolymerization process, including extend the reaction time and increase 1234yf monomer feeds.

Embodiment 19 is to 22-TFE-1234ze copolymers

Into 400mL Hastelloy C oscillating tubes load distilled water (180mL),FS-10(5.30g)、 Disodium hydrogen phosphate (1.3g) and ammonium persulfate (0.16g), cooling, is emptied and nitrogen is rinsed.Then four are loaded into oscillating tube PVF (45g) and 1,3,3,3- tetrafluoropropenes (5g).Start being aggressively shaken for oscillating tube, and continue in whole service. Oscillating tube is heated to 70 DEG C, so that the pressure in autoclave increases to 543psi (1.1 to 3.7MPa) from 156.In pressure Stopping in 33 minutes is shaken and heated after reducing by 20% to 434psi (3.0MPa).This produces polymer emulsion, polymer breast Liquid by adding 100ml saturation MgSO with vigorous stirring₄The aqueous solution and condense.The polymer of precipitation is collected by filtration, And washed for several times with warm water (70 DEG C).After being dried 24 hours in 80 DEG C of vacuum drying ovens (100mmHg), 18g whites are obtained poly- Compound.

Polymer analysis：

DSC, 10 DEG C/min, N₂, second of heating：Tm is 306.5 DEG C

Composition¹⁹F NMR (mole %)：TFE/1,3,3,3- tetrafluoropropene copolymers (98/2)

Identical experimental arrangement is applied to embodiment 20 to 22, and the results are shown in Table 4.

Table 4：TFE-1,3,3,3- tetrafluoropropene copolymers

Above-mentioned Polymerization Example 19 to 22 is repeated, difference is that replace 1234ze with HFP uses to show to work as 1234ze replace HFP when copolymerization faster.As a result it is shown in Table 5.

Table 5：TFE-HFP copolymers

The copolymer of embodiment 19 to 22 all insoluble in varsol, including be heated to 75 to 100 DEG C DMF and DMAC。

By TFE-1,3,3,3- tetrafluoropropene copolymers (table 4) are compared with TFE-HFP copolymers (table 5), based on NMR Data, TFE/1,3,3,3- tetrafluoropropene copolymers are preferably combined than HFP with TFE.Used using the HFP copolymerization ratios carried out Higher proportion of HFP chargings in reactor are needed during 1234ze.TFE-1, the copolymer of 3,3,3- tetrafluoropropenes passes through higher 5 weight % losses than TFE-HFP copolymer more thermal-stable, the temperature for the copolymer containing 1234ze is at least used to contain It is made up of most 8 or 10 moles of % 1234ze.

Embodiment 23：1234ze/VF₂The fluoroelastomer of/TFE/PMVE copolymers

Prepare this by carrying out semi-batch emulsion polymerisation process at 80 DEG C in the reaction vessel being sufficiently stirred for and contain Fluoroelastomer.The sodium octyl of 1.75g seven water disodium hydrogen phosphates and 0.42g is dissolved in 1350g deionized deoxidation Water prepares the aqueous solution.From the solution, 1250g is encased in 2 liters of reactors.Solution is heated to 80 DEG C.Remove trace Oxygen after, with the perfluor of 35.9 weight % vinylidene fluoride (VF2), 8.3 weight % HFO-1234ze, 50.8 weight % Reactor is forced into by the monomer mixture of (methyl vinyl ether) (PMVE) and 5.0 weight % tetrafluoroethene (TFE) 320psig(2.2MPa).Then 4.0 weight % ammonium persulfate and 9.6 weight % seven water disodium hydrogen phosphate initiators are added The 40ml samples of the aqueous solution.When reactor pressure declines, by 49.3 weight % VF in whole polymerization₂, 3.1 weight % HFO1234ze, 39.4 weight % PMVE and 12.2 weight % TFE monomer mixture are fed in reactor to keep 320psig (2.2MPa) pressure.Additional initiator solution is added to keep polymerization rate.417g increments are altogether fed After monomer, stop monomer addition, and the residual monomer in purge reactor.Total reaction time is 2.2 hours.Gained is fluorine-containing Elastomer latices have 25.4 weight % solids content and 6.0 pH.Fluoroelastomer latex is coagulated with aluminum potassium sulfate solution Knot, is washed with deionized and dries.The Tg of copolymer is -24.1 DEG C and VF₂/ TFE/1234ze/PMVE composition (NMR¹H and¹⁹F) in terms of mole %=48.9/24.3/24.1/2.7.

Copolymer is compounded, O-ring is molded as, suppresses and solidify afterwards, is then compressed deformation test, to show altogether 1234ze comonomers in polymers are in the curing process as the function of cure sites.The O-ring of solidification passes through in rubber-like And elastomer behavior is presented by pressure-resistant compression deformation.

Copolymer is compounded with the ratio (parts by weight) shown in table 6 on twin-screw extruder.The solidification of the composition of compounding Characteristic is shown in Table 7.

O-ring by the press curing at 177 DEG C, then under a nitrogen at 232 DEG C solidify afterwards 16 hours and be made.

Table 6：The composition of compounding

RCR 6190 is BPP (34.4 weight %) and double (phenol)-AF (65.6 weight %) mixing Thing.VC-50 is 4,4 '-[2,2,2- tri- fluoro- 1- (trifluoromethyl-ethylidine] diphenol (about 62 weight %) and benzyltriphenylphosphonium- The mixture of 4,4- [three fluoro- 1- trifluoromethyls) ethylidene] two phenates (1: 1) (about 38 weight %).

Under the following conditions, using the instrument initial measurement curing characteristics of Monsanto MDR 2000：

Mobile die head frequency：1.66Hz；

Amplitude of fluctuation：± 0.5 degree

Temperature：165 DEG C or 177 DEG C

Test time：30 minutes

Tc90：Reach 90% time of peak torque, minute

The compression of O-ring sample is determined according to ASTM D395-89,70 hours at 200 DEG C, at 200 DEG C 168 hours, the deflection 25% in 70 hours at 225 DEG C.Average value is reported in Table 7.

Table 7：Compression (C/S) test result

Above-mentioned test result shows that fluoroelastomer shows good elastomer due to the full cross-linked density of solidification Characteristic.Above-mentioned solidification process, including moulded with mixing, it is adaptable to fluoroelastomer copolymer of the invention.

Embodiment 24：1234ze/VF₂The fluoroelastomer of/PMVE/TFE copolymers

Prepare this by carrying out semi-batch emulsion polymerisation process at 80 DEG C in the reaction vessel being sufficiently stirred for and contain Fluoroelastomer.The sodium octyl of 1.75g seven water disodium hydrogen phosphates and 0.42g is dissolved in 1350g deionized deoxidation Water prepares the aqueous solution.From the solution, 1250g is encased in 2 liters of reactors.Solution is heated to 80 DEG C.Remove trace Oxygen after, with the perfluor first of 8.1 weight % vinylidene fluoride (VF2), 44.4 weight % HFO1234ze, 44.7 weight % Reactor is forced into 320psig by the monomer mixture of base vinyl ethers (PMVE) and 2.8 weight % tetrafluoroethene (TFE) (2.2MPa).Then 4.0 weight % ammonium persulfate and 9.6 weight % seven water disodium hydrogen phosphate initiator solutions are added 40ml samples.When reactor pressure declines, by 18.9 weight % VF in whole polymerization₂, 34.2 weight % HFO- 1234ze, 36.8 weight % PMVE and 10.1 weight % TFE monomer mixture are fed in reactor to keep 320psig (2.2MPa) pressure.Additional initiator solution is added to keep polymerization rate.417g increments are altogether fed After monomer, stop monomer addition, and the residual monomer in purge reactor.Total reaction time is 13 hours.Gained is fluorine-containing Elastomer latices have 6.0 weight % solids content and 3.3 pH.Fluoroelastomer latex is coagulated with aluminum potassium sulfate solution Knot, is washed with deionized and dries.The Tg of copolymer is less than 0 DEG C and VF₂/ TFE/1234ze/PMVE composition (NMR¹H With¹⁹F) in terms of mole %=33.2/12.9/37.9/16.0.

Embodiment 25 to 28：1234ze/TFE/VF₂Copolymer

Into 400mL Hastelloy C oscillating tubes load distilled water (220mL),FS-10(5.30g)、 Disodium hydrogen phosphate (1.3g) and ammonium persulfate (0.16g), cooling, is emptied and nitrogen is rinsed.Then load inclined into oscillating tube Difluoroethylene (3.125g), tetrafluoroethene (50g) and 1,3,3,3- tetrafluoropropenes (9.4g).Start being aggressively shaken for oscillating tube, And continue in whole service.Oscillating tube is heated to 70 DEG C, so that the pressure in autoclave increases to 600psi from 260 (1.8 to 4.1MPa).Stop within 30 minutes shaking and heating after pressure reduces by 20% to 480psi (3.3MPa).This produces poly- Compound emulsion, the polymer emulsion is condensed by adding the 100ml saturation MgSO4 aqueous solution with vigorous stirring.Pass through mistake The polymer of precipitation is collected in filter, and is washed for several times with warm water (70 DEG C).Dried 24 hours in 80 DEG C of vacuum drying ovens (100mmHg) Afterwards, 30g white polymer is obtained.

Polymer analysis：

DSC, 10 DEG C/min, N₂, second of heating：Tm is 180 DEG C

Composition¹⁹F NMR (mole %)：VF₂/ TFE/1,3,3,3- tetrafluoropropene terpolymers

(18/80/2)

Identical experimental arrangement is applied to embodiment 26 to 28, and the results are shown in Table 8.

Table 8：TFE-1,3,3,3 tetrafluoropropene-VF₂Terpolymer

Copolymer does not dissolve in varsol, including is heated to 75 to 100 DEG C of DMF and DMAC.

Embodiment 29 to 32：1234ze/TFE/ ethylene copolymers

Into 400mL Hastelloy C oscillating tubes load distilled water (220mL),FS-10(5.30g)、 Disodium hydrogen phosphate (1.3g) and ammonium persulfate (0.16g), cooling, is emptied and nitrogen is rinsed.Then second is loaded into oscillating tube Alkene (3.125g), tetrafluoroethene (50g) and 1,3,3,3- tetrafluoropropenes (9.4g).Start oscillating tube to be aggressively shaken, and Continue in whole service.Oscillating tube is heated to 70 DEG C so that the pressure in autoclave from 260 increase to 764psi (1.8 to 5.1MPa).Stop within 60 minutes shaking and heating after pressure reduces by 20% to 321psi (4.1MPa).This produces polymer breast Liquid, the polymer emulsion is condensed by adding the 100ml saturation MgSO4 aqueous solution with vigorous stirring.It is collected by filtration The polymer of precipitation, and washed for several times with warm water (70 DEG C).After being dried 24 hours in 80 DEG C of vacuum drying ovens (100mmHg), obtain Obtain 20g white polymer.

Polymer analysis：

DSC, 10 DEG C/min, N2, second of heating：Tm is 200 DEG C

Constitute 19F NMR (mole %)：TFE/1,3,3,3- tetrafluoropropenes/ethylene-dien terpolymer

(3/94/3)

Identical experimental arrangement is applied to embodiment 30 to 32, and the results are shown in Table 9.

Table 9：TFE-1,3,3,3 tetrafluoropropenes-ethylene-dien terpolymer

Copolymer 29 and 30 shows crystallinity (Tm, but without Tg), and the copolymer of embodiment 31 and 32 is without fixed (without the Tm, but with Tg) of shape, and the film be formed as available for coated substrate can be melted.

When the combination of 1234ze and ethene increases to 25 moles of % (embodiments 31) from 15 moles of % (embodiment 30), institute Obtain copolymer and be changed into amorphous from crystallinity is shown.Most of this change is attributed to 1234ze presence, because its point Sub- size is bigger than ethene.Preferably, in 1234ze/TFE/ ethylene copolymers and 1234ze/TFE/HFP/ ethylene copolymers 1234ze and ethene are combined as at least 20 moles % to obtain the copolymer of amorphous state.

Embodiment 33：CTFE/ ethene/1234ze copolymers

Into 1L autoclaves load distillation deoxygenated water (500mL),FS-10 (5.30g), disodium hydrogen phosphate (1.3g) and ammonium persulfate (0.16g), cooling, is emptied and nitrogen is rinsed.Then ethene is loaded into autoclave at 0 DEG C (40g), CTFE (200g) and 1,3,3,3 tetrafluoropropenes (3g).Autoclave is stirred and heated to 70 DEG C and continues 2 hours.This production Raw polymer emulsion, the polymer emulsion by adding 150ml saturation MgSO with vigorous stirring₄The aqueous solution and condense.It is logical The polymer of precipitation is collected by filtration, and is washed for several times with warm water (70 DEG C).Dried in 80 DEG C of vacuum drying ovens (100mmHg) After 24 hours, 25g white polymers are obtained.

DSC, 10 DEG C/min, N2, second of heating：Tm is 241 DEG C

Composition¹⁹F NMR (mole %)：Ethene/CTFE/1,3,3,3 tetrafluoropropene terpolymers (47/51/2).

Claims

1. copolymer, it includes 1,3,3,3- tetrafluoropropenes and one or more comonomers in the following：Fluorine second Alkene, vinylidene fluoride, tetrafluoroethene, CTFE, hexafluoropropene and perfluor (alkyl vinyl ether), wherein the alkyl contains There is 1 to 5 carbon atom.

2. copolymer according to claim 1, wherein the copolymer is fluoroelastomer.

3. copolymer according to claim 2, wherein described 1,3,3,3- tetrafluoropropenes is in the fluoroelastomers Cure sites.

4. copolymer according to claim 1, wherein in the copolymer, described 1,3,3,3- tetrafluoropropenes replace institute State some or all of hexafluoropropene and exist.

5. copolymer according to claim 4, it includes the tetrafluoroethene and 1,3,3, the 3- tetrafluoropropene.

6. copolymer according to claim 1, it includes described 1,3,3,3- tetrafluoropropenes and the PVF.

7. copolymer according to claim 6, wherein described 1 in the copolymer, the amount of 3,3,3- tetrafluoropropenes is At least 18 moles %.

8. copolymer according to claim 1, wherein the copolymer includes described 1,3,3,3- tetrafluoropropenes, the fluorine Ethene and the tetrafluoroethene.

9. copolymer according to claim 8, wherein described the 1 of 100 moles of % 0.5 to 25 mole of % altogether is reached, The tetrafluoroethene of 3,3,3- tetrafluoropropenes, 15 to the 85 moles of % PVF and 10 to 80 weight % is present in described In copolymer.

It is 3,3,3- tetrafluoropropenes, described wherein the copolymer includes described 1 10. copolymer according to claim 1 Tetrafluoroethene, the vinylidene fluoride and the optional hexafluoropropene.

It is 3,3,3- tetrafluoropropenes, described wherein the copolymer includes described 1 11. copolymer according to claim 1 Tetrafluoroethene and the optional hexafluoropropene, described 1,3,3,3- tetrafluoropropenes and if there is hexafluoropropene combination Measure as 1 to 10 mole of %, and described 1,3,3,3- tetrafluoropropenes and if there is each of hexafluoropropene with least 0.1 mole of % amount is present, and the tetrafluoroethene exists with 90 to 99 moles of % amount, based on described 1,3,3,3- tetrafluoro third Alkene, the tetrafluoroethene and if there is the hexafluoropropene combination mole % meter reach 100 moles of % altogether.

12. copolymer according to claim 1, it includes described 1,3,3,3- tetrafluoropropenes, the tetrafluoroethene and second Alkene, and optional perfluorobutyl ethylene.

13. copolymer according to claim 1, it includes described 1,3,3,3- tetrafluoropropenes, the CTFE and Ethene, and the optional tetrafluoroethene and/or hexafluoro-isobutene.

14. copolymer according to claim 1, it includes described 1 as fluoroelastomer, 3,3,3- tetrafluoropropenes, with And any one of the vinylidene fluoride or the perfluor (alkyl vinyl ether).

15. copolymer according to claim 14, it includes the vinylidene fluoride, the tetrafluoroethene, and optionally The hexafluoropropene.

16. copolymer according to claim 15, it additionally comprises the perfluor (alkyl vinyl ether).

17. copolymer according to claim 14, it includes described 1,3,3,3- tetrafluoropropenes, the tetrafluoroethene and institute State perfluor (alkyl vinyl ether).